Substituted guanidine derivatives

ABSTRACT

The present application relates to novel guanidine derivatives of the formula (I)                    
     in which 
     R 1  represents a five- or six-membered heterocyclic group; 
     R 2  represents hydrogen or alkyl, 
     R 3  represents the groupings —OR 4 , —OCOR 5 , —OCOOR 6 , —OCONR 7 R 8  and —OSO 2 R 9 , where 
     R 4 , R 5  and R 6  independently of one another represent alkyl, alkoxyalkyl, halogenoalkyl, alkenyl, alkinyl, alkylaminoalkyl, dialkylaminoalkyl, optionally substituted cycloalkyl and in each case optionally substituted phenyl or benzyl, 
     R 7  and R 8  independently of one another represent hydrogen, alkyl, alkenyl and in each case optionally substituted phenyl or benzyl and 
     R 9  represents alkyl or optionally substituted phenyl, 
     A represents the groupings —CH 2 CH 2 —, (CH 2 ) 3  and —CH═CH— and 
     z represents cyano or nitro, 
     with the proviso that, if Z represents NO 2  and A represents —CH 2 CH 2 —, the radical R 2  represents hydrogen; and the compound of the formula (I) in which 
     R 1                     
     R 2  H, 
     R 3  OCH 3 , 
     A —CH 2 CH 2 — and 
     Z NO 2  is excluded. 
     The compounds serve for controlling insects, arachnids and nematodes.

TECHNICAL FIELD OF THE INVENTION

The present application relates to novel guanidine derivatives, to aprocess for their preparation and to their use for controlling animalpests.

BACKGROUND OF THE INVENTION

Is already known that certain heterocyclic compounds have insecticidalproperties (cf., for example, EP-A 0 192 060, EP-A 0 277 317, Literaturereferences according to CA 125, 188 277; 121, 255 796; 121, 157 642).

However, in particular at low application rates and concentrations, theactivity and/or activity spectrum of these compounds is not entirelysatisfactory in all areas of use.

DETAILED DESCRIPTION OF THE INVENTION

This invention, accordingly, provides novel guanidine derivatives of theformula (I)

in which

R¹ represents a five- or six-membered heterocyclic grouping whichcontains 1, 2, 3 or 4 nitrogen atoms and/or one or two oxygen or sulphuratoms as heteroatom ring members—where the number of heteroatoms is 1,2, 3 or 4- and which is optionally substituted by halogen, cyano, nitro,alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkinyl, alkoxy,halogenoalkoxy, alkenyloxy, halogenoalkenyloxy, alkinyloxy, alkylthio,halogenoalkylthio, alkenylthio, halogenoalkenylthio, alkinylthio,alkylsinphinyl, halogenoalkylsinphinyl, alkylsulphonyl,halogenoalkylsulphonyl, amino, alkylamino, dialkylamino, aryl, arylthio,arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl,alkylcarbonyl and/or alkoxycarbonyl;

R² represents hydrogen or alkyl,

R³ represents the groupings —OR⁴, —OCOR⁵, —OCOOR⁶, —OCONR⁷R⁸ and—OSO₂R⁹, where

R⁴, R⁵ and R⁶ independently of one another represent alkyl, alkoxyalkyl,halogenoalkyl, alkenyl, alkinyl, alkylaminoalkyl, dialkylaminoalkyl,optionally substituted cycloalkyl and in each case optionallysubstituted phenyl or benzyl,

R⁷ and R⁸ independently of one another represent hydrogen, alkyl,alkenyl and in each case optionally substituted phenyl or benzyl and

R⁹ represents alkyl or optionally substituted phenyl,

A represents the groupings —CH₂CH₂—, (CH₂)₃ and —CH═CH— and

z represents cyano or nitro,

with the proviso that, if Z represents NO₂ and A represents —CH₂CH₂—,the radical R² represents hydrogen; and the compound of the formula (I)in which

R¹

R² H,

R³ OCH₃,

A —CH₂CH₂— and

Z NO₂

is excluded.

Furthermore, it has been found that the compounds of the formula (I) areobtained when compounds of the formula (II)

in which

R¹, A and Z are as defined above

are reacted with halogen compounds of the formula (III)

in which

R² and R³ are as defined above and

x represents halogen (in particular chlorine or bromine),

in the presence of a base and if appropriate in the presence of adiluent.

Finally, it has been found that the novel compounds of the formula (I)have highly pronounced biological properties and are suitable especiallyfor controlling animal pests, in particular insects, arachnids andnematodes, encountered in agriculture, in forests, in the protection ofstored products and materials and in the hygiene sector.

The formula (I) provides a general definition of the compounds accordingto the invention.

Preferred substituents or ranges of the radicals listed in the formulaementioned above and below are illustrated below.

R¹ preferably represents a five- to six-membered heterocyclic groupingfrom the group consisting of pyrazolyl, 1,2,4-triazolyl, oxazolyl,isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl,pyrazinyl and pyrimidinyl, which is optionally substituted by fluorine,chlorine, bromine, cyano, nitro, C₁-C₂-alkyl (which is optionallysubstituted by fluorine and/or chlorine), C₁-C₂-alkoxy (which isoptionally substituted by fluorine and/or chlorine), C₁-C₂-alkylthio(which is optionally substituted by fluorine and/or chlorine), orC₁-C₂-alkylsulphonyl (which is optionally substituted by fluorine and/orchlorine),

R² preferably represents hydrogen or C₁-C₆-alkyl,

R³ preferably represents the groupings —OR⁴, —OCOR⁵, —OCOOR⁶, —OCONR⁷R⁸and —OSO₂R⁹, where

R⁴, R⁵ and R⁶ independently of one another preferably representC₁-C₁₂-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-halogenoalkyl having 1 to5 identical or different halogen atoms, such as fluorine, chlorine andbromine atoms; C₂-C₄-alkenyl, C₂-C₄-alkinyl,C₁-C₄-alkylamino-C₁-C₄-alkyl, di(C₁-C₄)-alkylamino-C₁-C₄-alkyl,represent C₃-C₆-cycloalkyl which is optionally mono- to trisubstitutedby identical or different substituents, preferred substituents which maybe mentioned being: halogen, C₁-C₄-alkyl and C₁-C₄-halogenoalkyl having1 to 5 identical or different halogen atoms, such as F, Cl and Br atoms,or represent phenyl or benzyl, each of which is optionally mono- totrisubstituted by identical or different substituents, preferred phenylsubstituents being in each case: halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy andC₁-C₄-halogenoalkyl and C₁-C₄-halogenoalkoxy having in each case 1 to 5identical or different halogen atoms, such as fluorine, chlorine andbromine atoms and nitro.

R⁷ and R⁸ independently of one another preferably represent hydrogen,C₁-C₆-alkyl, C₂-C₄-alkenyl or represent phenyl or benzyl, each of whichis mono- to trisubstituted by identical or different substituents,preferred phenyl substituents being in each case: halogen, C₁-C₄-alkyl,C₁-C₄-alkoxy and C₁-C₄-halogenoalkyl and C₁-C₄-halogenoalkoxy having ineach case 1 to 5 identical or different halogen atoms, such as fluorine,chlorine and bromine atoms; and

R⁹ preferably represents C₁-C₄-alkyl or represents phenyl which is mono-to trisubstituted by identical or different substituents, possiblesubstituents being: halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy andC₁-C₄-halogenoalkyl and C₁-C₄-halogenoalkoxy having in each case 1 to 5identical or different halogen atoms, such as fluorine, chlorine andbromine atoms,

A preferably represents the groupings —CH₂CH₂—, —(CH₂)₃— and —CH═CH—.

z preferably represents cyano or nitro,

with the proviso that, if Z represents NO₂ and A represents —CH₂CH₂—,the radical R² represents hydrogen; and the compound of the formula (I)in which

R¹

R² H, R³ OCH₃,

A —CH₂CH₂— and

Z NO₂

is excluded.

R¹ particularly preferably represents 6-chloro-3-pyridyl(6-chloro-pyridin-3-yl) or represents 2-chloro-5-thiazolyl(2-chloro-thiazol-5-yl),

R² particularly preferably represents hydrogen or C₁-C₅-alkyl,

R³ particularly preferably represents the groupings —OR⁴, —OCOR⁵,—OCOOR⁶, —OCONR⁷R⁸ and —OSO₂R⁹, where

R⁴, R⁵ and R⁶ independently of one another particularly preferablyrepresent C₁-C₈-alkyl, C₁-C₂-alkoxy-C₁-C₂-alkyl, C₁-C₂-halogenoalkylhaving 1 to 2 identical or different halogen atoms, such as fluorine,chlorine and bromine atoms; allyl, propargyl,C₁-C₂-alkylamino-C₁-C₂-alkyl, di(C₁-C₂)-alkylamino-C₁-C₂-alkyl,cyclopropyl, cyclopentyl, cyclohexyl or represent phenyl or benzyl, eachof which is optionally mono- to disubstituted by identical or differentsubstituents, possible phenyl substituents being in each case: fluorine,chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxyand nitro.

R⁷ and R⁸ independently of one another particularly preferably representhydrogen, C₁-C₄-alkyl, vinyl, allyl or represent phenyl or benzyl, eachof which is optionally mono- to disubstituted by identical or differentsubstituents, possible phenyl substituents being in each case: fluorine,chlorine, bromine, methyl, methoxy, trifluoromethyl andtrifluoromethoxy; and

R⁹ particularly preferably represents methyl, ethyl or phenyl which isoptionally mono- to disubstituted by identical or differentsubstituents, possible substituents being: fluorine, chlorine, bromine,methyl, methoxy, trifluoromethyl and trifluoromethoxy,

A particularly preferably represents the groupings —CH₂CH₂— and —CH═CH—,

Z particularly preferably represents cyano or nitro,

with the proviso that, if Z represents NO₂ and A represents —CH₂CH₂—,the radical R² represents hydrogen; and the compound of the formula (I)in which

R¹

R² H,

R³ OCH₃,

A —CH₂CH₂— and

Z NO₂

is excluded.

Preferred compounds according to the invention are substances of theformulae (IA) to (ID):

in which

R², R³ and Z have the general, preferred and particularly preferredmeanings mentioned above.

Preferred compounds according to the invention are also substances ofthe formulae (IA-1), (IA-2), (IB-1), (IB-2), (IC-1), (IC-2), (ID-1) and(ID-2):

in which

R³ has the general, preferred and particularly preferred meaningsmentioned above.

The abovementioned general or preferred radical definitions orillustrations apply to the end products and, correspondingly, to thestarting materials and intermediates. These radical definitions can becombined with one another as desired, i.e. including combinationsbetween the respective preferred ranges.

Preference according to the invention is given to the compounds of theformula (I) which contain a combination of the meanings listed above asbeing preferred (preferable).

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being particularly preferred.

In the radical definitions given above and below, hydrocarbon chains,such as alkyl—including in combination with heteroatoms such asalkoxy—are in each case straight-chain or branched as far as this ispossible.

Using, for example,1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-imidazoline andi-propoxymethyl chloride as starting materials, the course of theprocess according to the invention can be represented by the followingreaction scheme:

The compounds of the formula (II) required as starting materials forcarrying out the process according to the invention are known (cf., forexample, EP-A 0 192 060, EP-A 0 235 725, EP-A 0 259 738 and EP-A 0 315826), and/or they can be obtained in the manner described therein.

The halogen compounds of the formula (III) further to be used asstarting materials in the process according to the invention aregenerally known compounds of organic chemistry and/or are obtainable bygenerally known methods.

The process according to the invention for preparing the novel compoundsof the formula (I) is preferably carried out using diluents. Suitablediluents are virtually all inert organic solvents. These preferablyinclude aliphatic and aromatic, optionally halogenated hydrocarbons suchas pentane, hexane, heptane, cyclohexane, petroleum ether, benzine,ligroin, benzene, toluene, xylene, methylene chloride, ethylenechloride, chloroform, carbon tetrachloride, chlorobenzene ando-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether,glycol dimethyl ether and diglycol di-methyl ether, tetrahydrofuran anddioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropylketone and methyl isobutyl ketone, esters, such as methyl acetate andethyl acetate, nitriles, such as, for example, acetonitrile andpropionitrile, amides, such as, for example, dimethylformamide,dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide,tetramethylene sulphone and hexamethylphosphoric triamide.

Bases which can be used in the process according to the invention areall customary proton acceptors. Preference is given to using alkalimetal or alkaline earth metal hydroxides, alkali metal or alkaline earthmetal hydrides, alkali metal or alkaline earth metal carbonates orbicarbonates or nitrogen bases. Examples which may be mentioned aresodium hydroxide, calcium hydroxide, sodium hydride, potassiumcarbonate, sodium bicarbonate, triethylamine, dibenzylamine,diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO),diazabicyclononene (DBN) and diazabicycloundecene (DBU).

The reaction temperatures in the process according to the invention canbe varied within a relatively wide range. In general, the process iscarried out at temperatures between —40° C. and +200° C., preferablybetween −10° C. and 100° C.

When carrying out the process according to the invention for preparingthe compounds of the formula (I), generally 1 to 3 mol, preferably 1 to2 mol, of the halogen compound of the formula (III) are employed permole of compounds of the formula (II).

Work-up and isolation of the end products are carried out in theconventional manner. The active compounds are suitable for controllinganimal pests, in particular insects, arachnids and nematodes,encountered in agriculture, in forests, in the protection of storedproducts and of materials, and in the hygiene sector, and have goodplant tolerance and low toxicity to warm-blooded animals. They maypreferably be used as crop protection agents. They are active againstnormally sensitive and resistant species and against all or some stagesof development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus humanus corporis,Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcomi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Spodoptera litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofinannophila pseudospretella,Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysiaambiguella, Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The phytoparasitic nematodes include Pratylenchus spp., Radopholussimilis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heteroderaspp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorusspp., Xiphinema spp., Trichodorus spp.

The compounds of the formula (I) according to the invention inparticular have high insecticidal activity.

They can be used particularly successfully for controllingplant-damaging leaf and soil insects, such as, for example, againstmosquito larvae (Aedes aegypti), against the black bean aphid (Aphisfabae), against the eggs of the onion fly (Hylemyia antiqua), againstthe peach aphid (Myzus persicae), against the green rice leaf-hopper(Neophotettix cincticeps), against the larvae of the mustard beetle(Phaedon cochleariae), and against the larvae of the army worm(Spodoptera frugiperda).

Additionally, the compounds according to the invention also haveroot-systemic action.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension emulsionconcentrates, natural and synthetic materials impregnated with activecompound and very fine encapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, if appropriate with the use of surfactants, that isemulsifiers and/or dispersants and/or foam-formers.

If the extender used is water, it is also possible to use, for example,organic solvents as auxiliary solvents. Suitable liquid solvents areessentially: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example mineral oilfractions, mineral and vegetable oils, alcohols such as butanol orglycol and their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals such as finely divided silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, and synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, maize cobs and tobacco stalks; suitable emulsifiers and/orfoam-formers are: for example nonionic and anionic emulsifiers, such aspolyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates; suitabledispersants are: for example lignin-sulphite waste liquors andmethylcellulose.

Tackifiers such as carboxyrnethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices such as gum arabic,polyvinyl alcohol and polyvinyl acetate, and natural phospholipids suchas cephalins and lecithins, and synthetic phospholipids, can be used inthe formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms prepared fromthese formulations as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphates, carbamates, carboxylates,chlorinated hydrocarbons, phenylureas and substances produced bymicroorganisms, inter alia.

Examples of particularly advantageous mixing components are thefollowing:

Fungicides:

aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone,

fluazinam, flumetover, fluoromide, fluquinconazole, flurprimidol,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl,furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

quinconazole, quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichiamide, tricyclazole, tridemorph,triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

(E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanoneO-(phenylmethyl)-oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrol-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropane-carboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrol-2,5-dione,

3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,

3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,

bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,

ethyl [(4-chlorophenyl)-azo]-cyanoacetate,

potassium hydrogen carbonate,

methanetetrathiol sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

N-(2-chloro4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,

N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,

N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methaneimidamide,

N-formyl-N-hydroxy-DL-alanine-sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran]-3′-one,

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin, AKD 1022,

Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb,buprofezin, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton S-methyl, diaeloden,diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermectin,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

H 5992

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb, TI 435,

vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

It is also possible to admix other known active compounds, such asherbicides, or fertilizers and growth-regulating substances.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercial formulationsand in the use forms prepared from these formulations, as a mixture withsynergists. Synergists are compounds which increase the activity of theactive compounds, without it being necessary for the added synergist tobe active itself.

The active compound content of the use forms prepared from thecommercial formulations can vary within wide ranges. The active compoundconcentration of the use forms can be from 0.0000001 to 95% by weight ofactive compound, and is preferably between 0.0001 and 1% by weight.

The application is carried out in a manner which is adapted to the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by excellent residual activity on wood andclay, and by good stability to alkali on limed substrates.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The compounds according to the invention have, for example, gooddevelopment-inhibitory action against fly larvae of Lucilia cuprina.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100 to10,000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds of the formula (I)according to the invention have a strong insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned as examples and as preferred—butwithout a limitation:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Emobius mollis,Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis,Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus,Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.Dinoderus minutus.

Hymenopterons, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.

Bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentaccording to the invention or mixtures comprising these are to beunderstood as meaning, for example: building timber, wooden beams,railway sleepers, bridge components, boat jetties, wooden vehicles,boxes, pallets, containers, telegraph poles, wood panelling, woodenwindows and doors, plywood, chipboard, joinery or wooden products whichare used quite generally in house-building or in building joinery.

The active compounds can be used as such, in the form of concentrates orin generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyestuffs and pigments, and also other processingauxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and timber products comprise the active compound according tothe invention in a concentration of 0.0001 to 95% by weight, inparticular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compound,based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flash point above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., turpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flash point above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture or an aliphatic polar organic chemicalsolvent or solvent mixture is replaced. Aliphatic organic chemicalsolvents containing hydroxyl and/or ester and/or ether groups, such as,for example, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin,silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fingicides, if appropriate.

Possible additional mixing components are, preferably, the insecticidesand fungicides mentioned in Wo 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing components which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and also fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and the use of the active compounds according to theinvention are illustrated by the examples below.

PREPARATION EXAMPLES Example 1

At 5° C., 1.5 g (0.0063 mol)1-(6-chloro-pyridin-3-yl-methyl)-2-cyanoimino-imidazolidine in 25 ml ofabsolute dimethylformamide are admixed with stirring with 0.25 g (0.0063mol) of sodium hydride, a little at a time. After 1 hour of stirring atroom temperature, 0.7 ml (0.0063 mol) of i-propoxymethyl chloride areadded at 0° C., and the mixture is stirred overnight. The reactionmixture is concentrated by distilling off the solvent and the residue istaken up in petroleum ether and filtered. The filtrate is purified bysilica gel column chromatography (methylene chloride/methanol: 15/0.5).

This gives 0.57 g (29% of theory) of1-(6-chloro-pyridin-3-yl-methyl)-2-cyanoimino-3-i-propoxymethyl-imidazolidineof melting point 85-87° C.

Example 2

With stirring, 1.5 g (5.7 mmol) of1-(2-chloro-thiazol-5-yl-methyl)-2-nitroimino-imidazolidine in 5 ml ofabsolute dimethylformamide are admixed a little at a time with 0.26 g(6.5 mmol) of sodium hydride. The mixture is stirred at room temperaturefor a short while, 0.70 g (6.5 mmol) of n-propoxymethyl chloride isadded with cooling and the mixture is stirred overnight. The reactionmixture is concentrated under reduced pressure and the residue isadmixed with water and extracted with methylene chloride. The organicphase is dried over sodium sulphate and concentrated and the residue isstirred with diisopropyl ether and reconcentrated.

This gives 1.54 g (76% of theory) of1-(2-chloro-thiazol-5-yl-methyl)-2-nitroimino-3-n-propoxymethyl-imidazolidineof calculated index n_(D) ²⁰=1.5781.

Example 3

At room temperature, 2.54 g (0.01 mol) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-imidazoline in 10 ml ofabsolute dimethylformamide are admixed, a little at a time, with 0.44 g(0.011 mol) of sodium hydride. The mixture is stirred for a short while,2.17 g (0.0125 mol) of bromoethoxymethyl chloride are added with coolingand the mixture is stirred at room temperature overnight. The reactionmixture is concentrated under reduced pressure and the residue isadmixed with water and extracted with methylene chloride. The organicphase is dried over sodium sulphate and concentrated and the residue isstirred in diisopropyl ether and filtered. The filtrate is purified bysilica gel column chromatography (methylene chloride/methanol: 10/1).

This gives 2.3 g (53% of theory) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-3-bromoethoxymethyl-imidazolineof melting point 90-92° C.

The compounds listed in Table 1 below are obtained analogously to thePreparation Examples 1 to 3 and in accordance with the generalstatements about the preparation of the compounds of the formula (I):

Physical const. (m.p. ° C.) or Ex. logP (pH = 2.3) No. R₁ A R₂ R₃ Z *) 4

—CH₂CH₂— H —OC₂H₅ NO₂ 66-69 5

—CH₂CH₂— H —OC₈H₁₇-n NO₂ 3.55 6

—CH═CH— H —OC₂H₅ NO₂ 1.09 7

—CH═CH— H —OC₈H₁₇-n NO₂ 101—03  8

—CH₂CH₂— H

NO₂  98-100 9

—CH═CH— H —OCH₃ NO₂ 0.78 10

—CH₂CH₂— H —OC₃H₇-n NO₂ 1.64 11

—CH═CH— H —OC₃H₇-n NO₂ 64-66 12

—CH₂CH₂— H —OC₃H₇-i NO₂ 70-71 13

—CH₂CH₂— H —OCH₂C₃H₇-i NO₂ 2.00 14

—CH═CH— H —OC₃H₇-i NO₂ 85-87 15

—CH═CH— H —OCH₂C₃H₇-i NO₂ 97-99 16

—CH₂CH₂— H —OCH₃ NO₂ 1.14 17

—CH₂CH₂— H —OC₂H₅ NO₂ 1.40 18

—CH₂CH₂— H —OC₃H₇-i NO₂ 1.65 19

—CH₂CH₂— H —OCH₂C₃H₇-i NO₂ 2.12 20

—CH₂CH₂— H —OCH₂C(CH₃)₃ NO₂  98-100 21

—CH₂CH₂— H —OC(CH₃)C₂H₅ NO₂ 1.86 22

—CH₂CH₂— H —OC₅H₁₁-n NO₂ 2.35 23

—CH₂CH₂— H —OC₆H₁₃-n NO₂ 2.73 24

—CH₂CH₂— H —OCH₂CH₂OCH₃ NO₂ 1.16 25

—CH₂CH₂— H —OCOC(CH₃)₃ NO₂ 118-20 26

—CH₂CH₂— H

NO₂ 134-35  27

—CH₂CH₂— H —OCH₂C₃H₇-i CN 77    28

—CH₂CH₂— H —OCH₂C(CH₃)₃ CN 132-33  29

—CH₂CH₂— H —OCH₃ CN 1.32 30

—CH₂CH₂— H —OCOC(CH₃)₃ CN 102-03  31

—CH₂CH₂— H —OCH₂CH₂OCH₃ CN 1.40 32

—CH₂CH₂— H —OC₃H₇-n CN 1.89 33

—CH₂CH₂— H —OCOCH₃ NO₂ 109-11  34

—CH₂CH₂— H

NO₂ 2.06 35

—CH₂CH₂— H —OCOC₂H₅ NO₂ 1.50 36

—CH₂CH₂— H —OCOC₃H₇-i NO₂ 82    37

—CH₂CH₂— H —OCOCH₃ CN 85-87 38

—CH₂CH₂— H —OCOC₂H₅ CN 75    39

—CH₂CH₂— H —OCOC₃H₇-i CN 85-86 40

—CH₂CH₂— H —OC₄H₉-n NO₂ 1.98 41

—CH═CH— H —OC₄H₉-n NO₂ 1.72 42

—CH₂CH₂— H

CN 113    43

—CH₂CH₂— H —OCH₂CH₂N(CH₂H₅)₂ NO₂ 0.70 44

—CH₂CH₂— H —OCH₂CH═CH₂ NO₂ 69-71 45

—CH₂CH₂— H —OCH₂C≡CH NO₂ 68-69 46

—CH₂CH₂— H

CN 122-24  47

—CH₂CH₂— H

NO₂ 144    48

—CH₂CH₂— H

NO₂ 137    49

—CH₂CH₂— H

CN 146    50

—CH═CH— H

NO₂ 144    51

—CH₂CH₂— H

NO₂ 141    52

—CH₂CH₂ H

NO₂ 110    53

—CH₂CH₂— H —O—(CH₂)₂—Br NO₂ 1.64 54

—CH₂CH₂— CH₃ —OC₃H₇-n NO₂ 93-95 55

—CH₂CH₂— H

NO₂ 102-05  56

—(CH₂)₃— H —OC₃H₇-i NO₂ 1.34 57

—(CH₂)₃— H —O—CO—C₄H₉-t NO₂ 143-44  58

—CH₂CH₂— CH₃ —O—CH₂—CH═CH₂ NO₂ 75-77 59

—CH₂CH₂— H

NO₂ 1.57

[logP=The logP values were determined in accordance with EEC directive79/831 Annex V. A8 by HPLC (gradient method, acetonitrile/0.1% aqueousphosphoric acid]

Use examples Example A

Aedes Test

Solvent: 1000 parts by weight of methanol

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water to the desired concentrations.

Mosquito larvae (Aedes aegypti) are placed into the preparation ofactive compound of the desired concentration.

After the desired period of time, the effect on the larvae isdetermined. 100% means that all animals exhibit serious symptoms or havebeen killed; 0% means that no animals have been killed.

In this test, at an exemplary active compound concentration of 0.0016%,the compounds of Preparation Examples 4, 5 and 7 effected a kill of100%, in each case after 4 hours.

Example B

Aphis Test (Systemic Action)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Vicia faba) which are heavily infested by the black beanaphid (Aphis fabae) are watered with in each case 20 ml of thepreparation of active compound of the desired concentration so that thepreparation of active compound penetrates into the soil without wettingthe shoot. The active compound is taken up by the roots and passed on tothe shoot.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshas been killed.

In this test, at an exemplary active compound concentration of 0.01%,the compounds of:

Preparation Examples 4 and 9 effected a kill of 100%

the Preparation Example 5 effected a kill of 95%

in each case after 4 days.

Example C

Hylemyia Test

Solvent: 100 parts by weight of acetone

1900 parts by weight of methanol

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with methanol to the desired concentration.

A stated amount of the preparation of active compound of the desiredconcentration is pipetted onto a standardized quantity of artificialfeed. After the methanol has evaporated, about 20 eggs of the onion fly(Hylemyia antiqua) are placed on the feed.

After the desired period of time, the kill of the eggs or larvae in % isdetermined. 100% means that all animals have been killed; 0% means thatnone of the animals has been killed.

In this test, at an exemplary active compound concentration of 0.05%,the compound of Preparation Example 4 effected a kill of 100% after 7days.

Example D

Myzus Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested by thepeach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshas been killed.

In this test, at an exemplary active compound concentration of 0.1%, thecompounds of Preparation Examples 10, 11, 12, 13, 14, 15, 16, 17, 18,20, 25 and 36 effected a kill of 100%, in each case after 6 days.

Example E

Nephotettix Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the green rice leaf-hopper (Nephotettixcincticeps) while the seedlings are still moist.

After the desired period of time, the kill in % is determined. 100%means that all leaf-hoppers have been killed; 0% means that none of theleaf-hoppers has been killed.

In this test, at an exemplary active compound concentration of 0.1%, thecompounds of Preparation Examples 4, 10, 12, 13, 14, 15, 18, 19, 21, 24,25, 26, 33 and 36 effected a kill of 100%, in each case after 6 days.

Example F

Phaedon larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with mustard beetle larvae (Phaedon cochleariae) whilst theleaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae has been killed.

In this test, at an exemplary active compound concentration of 0.1%, thecompounds of Preparation Examples 4, 10, 12, 17, 18, 19, 21, 25, 33, 34,35 and 36 effected a kill of 100, in each case after 7 days.

Example G

Spodoptera Frugiperda Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the army worm (Spodoptera frugiperda) whilstthe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all larvae have been killed; 0% means that none of the larvaehas been killed.

In this test, at an exemplary active compound concentration of 0.1%, thecompounds of Preparation Examples 2, 10, 12, 13, 17, 18, 20, 25, 33, 35and 36 effected a kill of 100, in each case after 7 days.

Example H

Spodoptera Frugiperda Test/arfificial Feed

Solvent: 100 parts by weight of acetone

1900 parts by weight of methanol

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with methanol to the desired concentration.

A stated amount of the preparation of active compound of the desiredconcentration is pipetted onto a standardized quantity of artificialfeed. After the methanol has evaporated, in each case one larva (L₂-L₃)of the army worm (Spodoptera frugiperda) is placed onto the feed, in 3repetitions.

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals has been killed.

In this test, at an exemplary active compound concentration of 0.05%,the compound of Preparation Example 4 effected a kill of 100% after 7days.

Example I

Critical Concentration Test/root-systemic Action

Test insect: Aphis fabae

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is mixed intimately with soil. Theconcentration of the active compound in the preparation is virtuallyimmaterial, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (=mg/l), matters. The treated soil isfilled into pots which are planted with pregerminated broad beans. Thus,the active compound can be taken up from the soil by the plant roots andtransported into the leaves.

To demonstrate the root-systemic effect, the leaves are populated withthe abovementioned test animals after 7 days. After a further 6 days,evaluation is carried out by counting or estimating the dead animals.The root-systemic action of the active compound is deduced from thenumber of animals killed. It is 100% when all test animals have beenkilled and 0% when the number of live test insects is identical to thatof the untreated control.

In this test, at an exemplary active compound concentration of 20 ppm,the compounds of Preparation Examples 4 and 5 effected a kill of 100%.

Example J

Blowfly Larvae Test/development-inhibitory Action

Test animals: Lucilia cuprina larvae

Solvent: Dimethyl sulfoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulfoxide,more dilute concentrations are prepared by dilution with Dest.H₂O.

About 20 Lucilia cuprina larvae are introduced into a test tube whichcontains about 1 cm³ of horse meat and 0.5 ml of the preparation ofactive compound to be tested. After 24 hours and 48 hours, theeffectiveness of the preparation of active compound is determined. Thetest tubes are transferred into beakers whose bottom is covered withsand. After a further 2 days, the test tubes are removed and the pupaeare counted.

The effect of the preparation of active compound is assessed by thenumber of flies which have hatched after 1.5 times the developmentperiod of an untreated control. 100% means that no flies have hatched;0% means that all flies have hatched normally.

In this test, at an exemplary active compound concentration of 100 ppm,the compounds of preparation examples 9, 10, 11, 12 and 13 exhibited adevelopment-inhibitory effect of 100%.

What is claimed is:
 1. A compound of the formula (I),

wherein R¹ represents a five- or six-membered heterocyclic groupselected from the group consisting of pyrazolyl, 1,2,4-triazolyl,oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl,pyridyl, pyrazinyl and pyrimidinyl, which is unsubstituted orsubstituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₂-alkylwhich is unsubstituted or substituted by a substituent selected from thegroup consisting of fluorine and chlorine, C₁-C₂-alkoxy which isunsubstituted or substituted by a substituent selected from the groupconsisting of fluorine and chlorine, C₁-C₂-alkylthio which isunsubstituted or substituted by a substituent selected from the groupconsisting of fluorine and chlorine, or C₁-C₂-alkylsulphonyl which isunsubstituted or substituted by a substituent selected from the groupconsisting of fluorine and chlorine, R² represents hydrogen orC₁-C₆-alkyl, R³ represents —OR⁴, —OCOR⁵, —OCOOR⁶, —OCONR⁷R⁸ or —OSO₂R⁹,wherein R⁴, R⁵ and R⁶ independently of one another each representsC₁-C₁₂-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-halogenoalkyl having 1 to5 identical or different halogen atoms, selected from the groupconsisting of fluorine, chlorine and bromine atoms, C₂-C₄-alkenyl,C₂-C₄-alkynyl, C₁-C₄-alkylamino-C₁-C₄-alkyl,di(C₁-C₄)-alkylamino-C₁-C₄-alkyl, represents C₃-C₆-cycloalkyl which isunsubstituted or mono- to trisubstituted by identical or differentsubstituents selected from the group consisting of halogen, C₁-C₄-alkyland C₁-C₄-halogenoalkyl having 1 to 5 identical or different halogenatoms, selected from the group consisting of F, Cl and Br atoms, orrepresent phenyl or benzyl, each of which is unsubstituted or mono- totrisubstituted by identical or different substituents, the phenylsubstituents being in each case selected from the group consisting ofhalogen, C₁-C₄-alkyl, C₁-C₄-alkoxy and C₁-C₄-halogenoalkyl andC₁-C₄-halogenoalkoxy having in each case 1 to 5 identical or differenthalogen atoms, selected from the group consisting of fluorine, chlorineand bromine atoms and nitro, R⁷ and R⁸ independently of one anotherrepresent hydrogen, C₁-C₆-alkyl, C₂-C₄-alkenyl or represent phenyl orbenzyl, each of which is mono- to trisubstituted by identical ordifferent substituents, the phenyl substituents being in each caseselected from the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxyand C₁-C₄-halogenoalkyl and C₁-C₄-halogenoalkoxy having in each case 1to 5 identical or different halogen atoms, selected from the groupconsisting of fluorine, chlorine and bromine atoms and R⁹ representsC₁-C₄-alkyl or represents phenyl which is mono- to trisubstituted byidentical or different substituents selected from the group consistingof halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy and C₁-C₄-halogenoalkyl andC₁-C₄-halogenoalkoxy having in each case 1 to 5 identical or differenthalogen atoms, selected from the group consisting of fluorine, chlorineand bromine atoms, A represents —CH₂CH₂—, z represents cyano or nitro,with the proviso that (i) if Z represents NO₂, the radical R² representshydrogen, and (ii) the compound of the formula (I) wherein R¹ represents

R² represents H, R³ represents OCH₃, A represents —CH₂CH₂— and zrepresents NO₂ is excluded.
 2. The compound of claim 1 wherein R¹represents 6-chloro-3-pyridyl (6-chloro-pyridin-3-yl) or represents2-chloro-5-hiazolyl (2-chloro-thiazol-5-yl), R² represents hydrogen orC₁-C₅-alkyl, R³ represents —OR⁴, —OCOR⁵, —OCOOR⁶, —OCONR⁷R⁸ or —OSO₂R⁹,wherein R⁴, R⁵ and R⁶ independently of one another each representsC₁-C₈-alkyl, C₁-C₂-alkoxy-C₁-C₂-alkyl, C₁-C₂-halogenoalkyl having 1 to 2identical or different halogen atoms, selected from the group consistingof fluorine, chlorine and bromine atoms, allyl, propargyl,C₁-C₂-alkylamino-C₁-C₂-alkyl, di(C₁-C₂)-alkylamino-C₁-C₂-alkyl,cyclopropyl, cyclopentyl, cyclohexyl or represent phenyl or benzyl, eachof which is unsubstituted or mono- to disubstituted by identical ordifferent substituents, the phenyl substituents being in each caseselected from the group consisting of fluorine, chlorine, bromine,methyl, methoxy, trifluoromethyl and trifluoromethoxy and nitro, R⁷ andR⁸ independently of one another represent hydrogen, C₁-C₄-alkyl, vinyl,allyl or represent phenyl or benzyl, each of which is unsubstituted ormono- to disubstituted by identical or different substituents, thephenyl substituents being in each case selected from the groupconsisting of fluorine, chlorine, bromine, methyl, methoxy,trifluoromethyl and trifluoromethoxy, and R⁹ represents methyl, ethyl orphenyl which is unsubstituted or mono- to disubstituted by identical ordifferent substituents selected from the group consisting of fluorine,chlorine, bromine, methyl, methoxy, trifluoromethyl andtrifluoromethoxy, A represents —CH₂CH₂—, z represents cyano or nitro,with the proviso that (i) if Z represents NO₂, the radical R² representshydrogen, and (ii) the compound of the formula (I) wherein R¹ represents

R² represents H, R³ represents OCH₃, A represents —CH₂CH₂— and zrepresents NO₂ is excluded.
 3. A composition for controlling animalpests selected from the group consisting of insects, arachnids andnematodes, comprising at least one compound-of the formula (I) accordingto claim 1 and one or more extenders and/or surfactants.
 4. A method forcontrolling animal pests selected from the group consisting of insects,arachnids and nematodes, comprising the step of allowing a compound ofthe formula (I) according to claim 1 to act on the pests and/or theirhabitat.
 5. A process for preparing a compound of the formula (I)

wherein R¹, R², R³, A and Z are as defined in claim 3, with the provisothat (i) if Z represents NO₂, the radical R² represents hydrogen, and(ii) the compound of the formula (I) wherein R¹ represents

R² represents H, R³ represents OCH₃, A represents —CH₂CH₂— and zrepresents NO₂ is excluded, said process comprising reacting a compoundof the formula (II)

wherein R¹, A and Z are as defined above with a halogen compound of theformula (III)

wherein R² and R³ are as defined above and x represents halogen, in thepresence of a base.
 6. The process of claim 5 wherein the reaction iscarried out in the presence of a diluent.
 7. The process of claim 5herein X represents a halogen selected from the group consisting ofchlorine and bromine.
 8. A process for preparing a composition forcontrolling animal pests selected from the group consisting of insects,arachnids and nematodes, comprising the step of mixing a compound of theformula (I) according to claim 1 with diluents and/or surfactants.